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 Chapter 1

Nanopowders Production and Micron-Sized Powders

Spheroidization in DC Plasma Reactors

Andrey Samokhin, Nikolay Alekseev,

Andrey Samokhin, Nikolay Alekseev,
Mikhail Sinayskiy, Aleksey
Mikhail Sinayskiy, Astashov,
Aleksey Astashov,
Dmitrii Kirpichev, Andrey Fadeev,
Dmitrii Kirpichev, Andrey Fadeev, Yurii Tsvetkov
Yurii Tsvetkov and
Andrei Kolesnikov
and Andrei Kolesnikov

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.76262

Abstract

Technology for metal and inorganic compounds nanopowders production in DC arc

plasma reactors has been developed. Similar DC arc plasma reactors were used for micron-
sized powders spheroidization. Results of experimental studies are presented. Formation
of nanoparticles via different mechanisms as well as mass transfer of nanopowders to the
reactor cooling surfaces are discussed. Heat flux distribution along the reactor wall and its
influence on the evolution of nanoparticles in the deposited layer are investigated. Effects
of plasma torch and confined jet reactor operation parameters on the granulometric,
phase and chemical composition of nanopowders are discussed. Potential of the confined
plasma jet apparatus for micron-sized metal and composite particles spheroidization is
demonstrated.

Keywords: thermal plasma, DC arc plasma torch, nanopowder, synthesis, reactor,

spheroidization, metals, inorganic compounds

1. Introduction

Nanosized powders of elements and their inorganic compounds are the basis for development
of various nanostructured materials. These materials include nanostructured functional ceram-
ics, hard alloys with increased wear resistance and toughness, dispersion hardened and mod-
ified structural alloys with enhanced performance characteristics, nanostructured protective

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
4 Powder Technology

thermo-, corrosion and wear-resistant coatings, polymer composites with fillers and inor-
ganic nanoparticle modifiers for alloys [1–9].

Various techniques are used for nanopowders synthesis, including processing in gas, liquid
and solid phases. Such methods employ physical and chemical deposition from gas phase,
precipitation from solutions, mechanical grinding, etc. The formation of nanoparticles by
homogeneous nucleation in supersaturated vapors followed by nanoparticles growth via
condensation and coagulation is the basis of any gas phase nanoparticles manufacturing pro-
cess. Fast cooling of saturated vapors or gas phase chemical reactions produce supersaturated
vapors. Depending on the method used, processes for nanopowders manufacturing in gas
phase include flame synthesis, evaporation in high-energy beams (laser radiation, accelerated
electrons, focused microwave radiation), and plasmachemical synthesis in DC arc plasma.

Plasmachemical synthesis is the most versatile method for manufacturing of metal and
inorganic compounds nanopowders, or nanopowders mixtures using inert, reducing and
oxidizing atmospheres with controlled composition. Main advantages of nanopowders plas-
machemical synthesis are:

1. Various types of nanopowders (individual elements, compounds and mixtures) can be

produced;

2. Physical and chemical characteristics of the nanopowders can be controlled and nanopow-
ders with required parameters (purity, chemical and phase compositions, specific surface)
can be produced;
3. Plasma reactors have small dimensions and high production rate;

4. Traditional commonly applied raw materials can be used;

5. Process can be easily scaled-up from laboratory setup to the level of industrial equipment
with high productivity.

High efficiency and other technological characteristics of nanopowder production in plasma

testify to the competitiveness of the plasma method and wide possibilities for its application.
As estimates show, the cost of nanopowders produced using plasma technologies at mass
production level should slightly differ from the cost of “traditional” powders of this nomen-
clature. Plasma technologies can be considered as an effective way of obtaining a wide range
of nanopowders. Thermal plasma can be generated using various types of electric discharges
[10]. They include DC arc discharge, high-frequency (radio frequency) induction plasma dis-
charge (RF), microwave plasma (UHF), as well as combined discharges.

At present, RF plasma reactors developed and manufactured by TEKNA [11] are widely used
for nanopowders production. When operating electrodeless RF and microwave plasmatrons,
the impurities (such as electrode’s erosion products) in the nanopowders are absent, but it
might appear when using DC arc plasma generators. However, it should be borne in mind
that the present value of 1 kW of power generated by RF and microwave plasma torches is up
to 3 times higher than the cost of plasma generation in DC arc plasma torches [12]. Besides,
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 5
http://dx.doi.org/10.5772/intechopen.76262

the power of modern DC arc plasma torches reaches 3–5 MW with a service life of up to 103 h
[13, 14], while the power of existing RF plasmatrons does not exceed 1 MW. The usage of
V-shaped DC arc plasmatrons where tungsten electrodes operate in an argon inert gas medium
[15] allows to minimize the presence of impurities of the electrode material in the thermal
plasma flow and to ensure the production of high-purity target products. Westinghouse
Plasma Corporation developed plasmatrons with a power of 300–2400 kW and thermal effi-
ciency of 70–85%. Such devices are used in waste materials processing and metallurgical fur-
naces operations [14]. DC plasma torches have high energy efficiency and can be used in
the realization of high-temperature processes on an industrial scale. This paper provides a
review of the research in the field of nanopowders synthesis and processing (spheroidization)
of micron sized powders in thermal plasma flows generated by DC arc plasma torches. The
research was carried out at the Institute of Metallurgy and Materials Science (IMET RAS) in
collaboration with partners over recent years.

2. Plasmachemical reactor

IMET RAS developed DC arc plasma torches with a nominal power of 30–150 kW with
self-setting arc length and gas discharge stabilization, as well as plasmatrons with an inter-
electrode insert. The torches were used for the generation of thermal plasma in IMET labora-
tories and pilot plants. The plasma torches operated with reducing, oxidizing and inert gases
and their mixtures and provided stable generation of plasma jets with an equilibrium tem-
perature of up to 4000–8000 K (for molecular gases) and up to 12,000 K (for monatomic gases).
The torches were used for both nanopowder production processes and for spheroidization
processes. Plasma synthesis of nanopowders includes a complex set of physicochemical pro-
cesses occurring in turbulent gas-dispersed non-isothermal flows. At present, plasma reactors
with confined jet are widely used for nanopowders production. In confined jet reactor, the
plasma jet flows into the volume of the reactor, which is confined by the cooled cylindrical
surface. The ratio of the torch nozzle diameter to the reactor’s diameter is of the order of 10.
The plasma jet can be generated by any type of plasma generator (DC arc discharge, high fre-
quency discharge, microwave discharge). When a plasma jet outflows from plasma torch into
reactor’s volume, a rapid temperature drop occurs, resulting in supersaturated vapors forma-
tion. Vapors condensation leads to the nanoscale particles formation. Evolution of nanopar-
ticles granulometric composition occurs in the reactor’s volume because of their condensation
and coagulation growth. Phase and chemical compositions of nanoparticles can also change.
Control of nanoparticles formation is achieved by variation of such operational parameters
as plasma jet chemical composition, enthalpy and flow rate; concentrations of reagents in the
reactor; and parameters of the reagents injection into the plasma jet. If solid powder is used
as raw material, the initial size of the solid particles has significant effect of nanoparticles
formation.

During nanoparticles formation in the volume of plasma reactor, they move toward internal
cooled surfaces of the reactor. The layer of nanoparticles is formed at these surfaces. The
deposited layer evolution is affected by heat flux from the high temperature gas flow inside
6 Powder Technology

the reactor. The evolution of nanoparticles in the layer is determined by the temperature dis-
tribution and lifetime of the layer, and the temperature distribution depends in turn on the
temperature of the cooled surface, the density of the mass flux of the deposited nanopar-
ticles, and the density of the heat flux passing through the layer. Under plasmachemical syn-
thesis conditions the layer thickness, as well as its thermal resistance, are increased in time.
The unsteady temperature field in the layer can lead to the time changes of the layer’s struc-
ture, phase and chemical composition. These changes are due to chemical reactions, phase
transformations, and particles sintering. All these changes occur when the temperature in
the growing layer increases. To obtain the nanopowder with required specifications, where
nanoparticles retain the properties determined by the conditions of their formation in the gas
stream, it is necessary to exclude or minimize the possibility of physicochemical transfor-
mations in the layer of precipitated particles. It is necessary to prevent the layer’s tempera-
ture rise above certain threshold values. These values are the temperatures of nanoparticles
characteristic chemical and phase transformations, and temperatures related to nanoparticles
growth due to their contacts in the layer. Nanoparticles are formed in the plasma process
inside the reaction zone, but possible nanoparticles transformations in the growing layer on
the reactor’s surfaces might change the properties of nanoparticles and become a problem.
This problem is important for the realization of controlled plasma synthesis of nanopowders
with given properties.
An unlimited growth of the nanoparticles layer thickness will inevitably lead to an increase in
the layer’s temperature resulting in the particles sintering and coarsening, as well as possible
change in their phase and chemical composition. These effects will be most pronounced for
nanoparticles with a low temperature of possible physicochemical transformations, especially
for particles with low melting point. Thus, to obtain the nanopowder with required specifica-
tions, the nanoparticles physical and chemical transformations in the deposited layer have to
be blocked. To achieve this, the thickness of this layer, formed on the stationary cooled reac-
tor’s surface, must be limited to a certain value. For particular target nanoproducts, the size of
the precipitating nanoparticles, the initial temperature of the deposition surface and the heat
flux density from the high temperature stream to the deposition surface will determine this
limiting layer’s thickness.

3. Heat transfer to the wall of reactor

The investigations of metal and inorganic compounds nanopowders synthesis included

experimental studies of heat and mass transfer in a confined plasma jet reactor [16].
Following topics were studied:

1. heat flux density distribution along the reactor‘s length to the nanoparticle deposition
surface

2. mass flux density distribution of deposited nanoparticles along the reactor‘s length
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 7
http://dx.doi.org/10.5772/intechopen.76262

3. physical and chemical properties of nanopowders deposited on the surface in various

zones under various process parameters

A cylindrical sectioned plasma reactor with confined jet stream was used. Reactor had diam-
eter and length of 200 and 600 mm correspondently (Figure 1) [17]. The length of the sections
varied in the range 70–130 mm. DC arc plasma torch with a rated power of 25 kW was used
for thermal plasma generation. Nitrogen, hydrogen-nitrogen mixture (22 vol. % H2), and air
were used as plasma-forming gases. The synthesized nanoparticles were deposited on the
reactor’s walls and partially removed with the exhaust gases into the filtration apparatus.

Figure 1. General view of 30 kW plasma setup.

8 Powder Technology

Following processes were carried out in the reactor:

• Copper nanopowders production via evaporation-condensation of dispersed copper (raw

particles less than 40 μm) in a nitrogen plasma;
• Production of tungsten nanopowders by reduction of dispersed tungsten trioxide WO3
(raw particles less than 40 μm) in hydrogen-nitrogen plasma
• Production of aluminum oxide nanopowders by oxidation of disperse aluminum (ASD-4,
raw particles less than 10 μm) in air plasma;
• Production of multicomponent composition in tungsten-carbon system (W-C) via interac-
tion of dispersed tungsten trioxide WO3 (raw particles less than 40 μm) with methane in
hydrogen-nitrogen plasma.

The reactions underlying these processes differ in thermal effects calculated under standard
conditions. Copper evaporation-condensation reaction has a zero thermal effect, the reaction
of tungsten trioxide reduction by hydrogen is weakly endogenous (0.5 MJ/kg WO3), and the
oxidation of aluminum by oxygen has a strong exogenous character (31 MJ/kg Al).

The experiments were carried out in the following parameters variation range:

Plasma forming gas flow rate 0.85–2 st. m3/hour,

Plasma torch nozzle diameter 6–12 mm,

Plasma flow enthalpy at the reactor inlet 13–29 MJ/st. m3,

Plasma flow power 6.6–12.3 kW,

Flow rate of dispersive raw material 1.0–7.0 g/min,

Duration of experiments 5–80 min

It was experimentally observed that when clean (no nanoparticles are present) nitrogen
plasma jet enters the reactor, the heat flux density distribution along the reactor’s length shows
maximum in the attachment region of the high-temperature flow to the reactor wall, which is
typical for the separated flows in the channels with sudden expansion. The value of the heat
flux density is determined mainly by the plasma flow power at the reactor’s inlet and in our
experiments it varied in the range 25–45 kW/m2. The maximum value of the heat flux density
exceeds by 2.5–3 times the values at initial and final sections of the reactor. Distribution of nor-
malized heat flux density, i.e. flux related to the magnitude of the maximum, remains prac-
tically unchanged in the whole experimental range of input parameters variation (thermal
power, flow rate and enthalpy) (Figure 2A). The presence of hydrogen in nitrogen practically
did not change the heat fluxes values in the reactor. A decrease of the torch nozzle diameter
from 10 mm to 6 mm led to the relocation of flow attachment region further downstream from
the reactor inlet, and location of maximum wall heat flux changed accordingly.

In experiments when nanopowders of copper, tungsten, and W-C composition were synthe-
sized, it was found that heat flux density distribution along the reactor length also had extre-
mum (Figure 2B), as in the case of the flow containing no dispersed particles. But for a two-phase
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 9
http://dx.doi.org/10.5772/intechopen.76262

flow (gas + particles) some increase in the heat flux density at the reactor initial sections was
observed. This may be due to the radiation from condensed particles to the wall in the highest
temperature zone of the reactor. This zone is located at the initial section of the plasma jet.
When aluminum oxide nanopowder was synthesized by oxidation of aluminum powder in
air plasma jet, the significant differences in heat fluxes distribution in comparison with other
realized processes were observed (Figure 3). With an increase in raw aluminum powder feed

Figure 2. Normalized heat flux and mass flux distributions at plasma reactor wall.
10 Powder Technology

Figure 3. Heat flux density distribution in Al2O3 nanopowder synthesis for various Al feed rates.

rate, the maximum heat flux density shifts toward the beginning of the reactor, while its mag-
nitude increases due to additional heat release as a result of the highly exogenous reaction of
aluminum oxidation by air oxygen. Depending on the raw material feed rate, the additional
power released as a result of this reaction was equal to 10–40% of the plasma jet power. The
local heat flux density on the reactor wall in the studied nanopowder syntheses varied in the
range 10–40 kW/m2. It follows from experiments that non-uniform wall heat flux density dis-
tribution exists in plasma reactor with a confined jet flow, and the exogenous reactions with a
pronounced thermal effect can exert a significant influence on the wall heat flux distribution.
Some nanoparticles degradation might occur inside the deposited nanoparticles layer in the
area of maximal heat flux.

4. Mass transfer to the wall of reactor and formation of particle’s layer

In the near-wall region of the plasma reactor, the nanoparticles transfer occurs under condi-
tions when the average size of the nanoparticles is smaller or commensurable with the mean
free path of the gas molecules, so the deposition of nanoparticles onto reactor wall from
turbulent non-isothermal flow will be determined by the resulting effect of thermophore-
sis and Brownian diffusion [18]. The performed experiments have demonstrated that the
deposited particles distribution along the reactor length has single extremum (Figure 2C),
while the location of the maximum particle mass flux density coincides with the location
of the maximum heat flux density. A similar particle flux density distribution is observed
for all the studied processes, including aluminum oxide synthesis, where heat flux density
distribution could have a bimodal character. The mass flow density is determined by the
condensed phase mass concentration in the solid–gas flow, with the maximum value of the
mass flow density exceeding by up to 2–3 times the mass flow density at the initial and final
sections of the reactor.

For all the processes in the studied parameter variation ranges a high degree of nanoparticles
deposition on the reactor surface is observed. The deposited mass is equal to 40–80% of the total
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 11
http://dx.doi.org/10.5772/intechopen.76262

mass of synthesized nanopowder. Consequently, the final properties of the produced nanopow-
ders are largely determined by the properties of the product that is precipitated exactly in the
reactor. The degree of nanoparticles deposition decreases with increasing of the process dura-
tion (thickness of the deposited layer of nanoparticles) and with an increase in the raw materials
feed rate (processing rate). It follows from analysis of experimentally found heat flux density
distributions and mass fluxes density distributions along the reactor wall that the maximum
heat flux position coincides with location of maximum mass flux, where growth of the nanopar-
ticle layer occurs at the maximum rate. The effect of heat flux makes possible nanoparticles
transformations such as sintering, chemical interaction with the active gaseous medium, and
phase transformations most probable exactly in this region of the reactor internal surface.
The layers of deposited nanoparticles had an extremely low bulk density, equal to 3–8% of the
theoretical density. The deposited layers thickness varied from 0.05 to 2.7 mm in the experi-
ments. Sintering of deposited nanoparticles near the maximum heat flux density location was
noted only for copper nanopowder, where the melting point of the metal is 1360 K. A slight
change in the average nanoparticle size inside the deposited layer along the reactor length
is noted for other nanopowders (W, Al2O3, (W-C)), whose materials have much higher melt-
ing point. General list of nanopowder syntheses, performed in confined jet reactor, is given
in Table 1. Some syntheses (AlN, AlON) were carried out in a combined reactor with dis-
perse raw materials pre-evaporation in a heat-insulated channel followed by gas chemical
quenching.

No Nanopowder Initial reagents Plasma Properties of nanopowders

forming gas
Phase composition Specific Impurities
surface
area,
m2/g
Metals

1 W, Mo, Ni, MexOy, H2, C3H8 + air H2 + N2, Me 2–30 [O]

Co, Re C3H8 + air

2 Cu CuCl H2 + N2 Cu, Cu2O, CuO, CuCl 2–5 [Cl], [O]

Cu(HCOO)2 N2 Cu, Cu2O, CuO 2–7 [C]

Cu(CH3COO)2 ∙ H2O N2 Cu, Cu2O, CuO 5–35 [C]

Cu(re-condensation) N2 Cu, Cu2O, CuO 20–36 [O]

Metal composites

3 W-Ni-Fe (W – WO3, NiO, Fe2O3, H2 H2 + N 2 W, Ni-Fe 5–12 [O]

95 mass %)

4 W-Cu (W - 80 WO3, CuO H2 + N 2 W, Cu 4–8 [O]

mass %)

5 Ag-SnO2 Ag, SnO2 air Ag, SnO2 4–25

Nitride, carbides, carbonitrides

6 TiN Ti, (TiH2), N2 N2 TiN 10–20 [Ti]metal

TiCl4, H2, N2 H2 + N 2 TiN 11–39 [Cl]

12 Powder Technology

No Nanopowder Initial reagents Plasma Properties of nanopowders

forming gas
Phase composition Specific Impurities
surface
area,
m2/g
7 AlN Al, NH3, N2 N2 AlN 75–100 [Al]metal

8 TiC TiCl4, H2, CH4 H2 + Ar TiC 15–45 [Cl]

9 TiCN TiCl4, H2, N2, CH4 H2 + N2 TiN 13–23 [Cl]

10 SiC SiCl4, H2, CH4 H2 + Ar Β - SiC 20–75 [Cl]

11 W – C (Ctotal = 6.2 WO3, CH4, H2 H2 + N2 WC1-x, W2C, W, C 15–25

mass %)

Oxides

12 Al2O3 Al, O2 Air δ – Al2O3 15–50

13 Al2O3 – MeO Al, Me, O2 Air MeAl2O4 (spinel) 12–16

(Me = Mg, Co)

14 AlON Al, NH3, N2, O2 N2 AlON 20–70 [Al] metal

15 TiO2 TiCl4, O2 O2 + Ar TiO2 (rutile + anatase) 10–120 [Cl]

16 SiO2 SiCl4, O2 O2 + Ar amorphous 200–300 [Cl]

17 ZrO2 ZrCl4, O2 O2 + Ar ZrO2 (monoclinic + 18–32 [Cl]

tetragonal)

18 ZrO2 – Al2O3 ZrCl4, Al, O2 O2 + Ar ZrO2 (tetragonal) 17 [Cl]

19 Y 2O 3 Y(COOH)3, O2 O2 + Ar Y2O3 (cubic) 15–25

Table 1. Nanoparticles syntheses.

5. Particle size distribution and morphology

Granulometric composition is one of the most important nanopowders characteristics, which

determines the possibility of their use in solving scientific problems and in practical applications.
According to the results of electron microscopy, all nanopowders synthesized in plasma reactor
are polydisperse and consist of particles of equiaxial shape (Figure 4). The presence of nanoob-
jects with oriented growth forms is not detected. Formation of nanoparticles under the condi-
tions of plasmachemical synthesis occurs through the macro-mechanisms “vapor–liquid-crystal”
(VLC), “vapor-crystal” (VC) and mixed mechanism, including a combination of these mecha-
nisms (VLC-VC). Thermodynamic calculations of the nanopowder equilibrium yield as a func-
tion of temperature elucidate the mechanism of nanoparticle formation in a particular process.

Suppose that the substance in question exists in the liquid and solid state, and its yield
depends on the temperature. Let us determine T* as the temperature corresponding to the
maximum yield of the nanoparticle substance, Tc as the maximum temperature at which the
nanoparticle exists in the condensed state, and Tm as the melting temperature of nanoparticle
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 13
http://dx.doi.org/10.5772/intechopen.76262

Figure 4. TEM and SEM micrographs. 1—Al2O3, 2—TiO2, 3—SiC, 4—W-C, 5—Cu, 6—W, 7—W-cu, 8—W-Ni-Fe, 9—TiC,
10—TiCN.
14 Powder Technology

matter. Taking into account the fact that the plasma process occurs at a decreasing tempera-
ture initially exceeding Tc, the temperature conditions for the nanoparticles formation by the
above-mentioned macro-mechanisms can be written as:
mechanism VLC, Тm < Т * < Тc, all particles have a spherical habit (Figure 5a; 4–1; 4–5);

mechanism VC, T* < Tc < Tm, all particles have a faceted habit (Figure 5b, 4–2);

mechanism of VLC-VC, T* < Tm < Tc, particles have both spherical and faceted habit (Figure 6c;
4–9; 4–10).

The VLC mechanism is realized if, under conditions of a decreasing process temperature,
the maximum yield of nanoparticle matter occurs at temperatures above the melting point
temperature (Figure 5a). The VC mechanism will determine formation of nanoparticles if the
formation occurs at the temperatures below the melting temperature of the nanoparticle mat-
ter (Figure 5b), or the substance does not exist at all in the liquid state.

If during nanoparticles formation temperature is reduced and the substance undergoes crys-
tallization (solidification) before the maximum yield is reached, then nanoparticles formation
mechanism changes from VLC to VC, and product will contain both spherical and faceted
particles (Figure 5c). As follows from the microphotographs of the obtained nanopowders
(Figure 4), nanoparticles formation in the realized plasma syntheses can occur through all three
of these mechanisms (VLC, VC, and VLC-VC). Under plasma synthesis conditions, all of the
above mechanisms took place in the formation of Al2O3, TiO2, Cu, W, TiN, TiCN and W-C com-
position nanoparticles. The micrographs of the nanopowders were used to construct the his-
tograms of the particle size distribution, and statistical analysis was carried out (Figure 6) [19].

It was established that the lognormal particle size distribution function (PSDF) reliably (with
a correlation coefficient of more than 0.95) describes all the objects under investigation over
wide range of changes in the granulometric composition of the investigated nanopowders.
In the PSDF formula d is the diameter of the particle, m is the median of the distribution, and σ is
the standard deviation. It should be emphasized, that the validity of lognormal particle size dis-
tribution was confirmed earlier for the case of nanopowders obtained in the processes where the
formation of particles occurs via coagulation mechanism, i.e. VLC [20]. The experimentally estab-
lished lognormal particle size distribution in the absence of coagulation growth in accordance

Figure 5. Possible characteristic relations between temperatures, when nanoparticles are formed via different mechanisms.
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 15
http://dx.doi.org/10.5772/intechopen.76262

with [21] can be due to the lognormal distribution of the particles residence time in the growth
zone. For the nanoparticles syntheses (Table 1) where formation of particles occurs through
various macro mechanisms, it has been experimentally established that the average size of the
nanoparticles increases with increasing concentration of the gas component precursor [22–30].
The effect of the plasma process parameters, as well as effect of the characteristic dimensions of
the reactor, was studied in Ref. [24] in case of tungsten and nickel nanopowders synthesis by
reduction of WO3 and NiO oxides in hydrogen-nitrogen and propane-air plasmas. It is shown
that the average metal nanoparticle size can be affected by the characteristic dimensions of the

Figure 6. Particles size distributions for Al2O3, TiO2, W, cu, TiCN and TiN nanopowders.
16 Powder Technology

plasma apparatus, such as reactor diameter and plasma torch nozzle diameter. These parameters
determine the dimensions of the high-temperature zone where the nanoparticles formation takes
place. The chemical processes, occurring at nanoparticle surface, also could influence the regu-
larities of nanoparticle growth. The results of studies of various nanopowders production in the
plasma reactor indicate that the influence of the process parameters on the average particle size
is a multifactor problem, where the physicochemical features of the process play significant role.

It was found that the average nanoparticle size depends on the synthesis parameters such as
the initial precursor concentration, plasma jet enthalpy and velocity. The individual features
of the specific process determine the degree of influence of these parameters. Production of
nanoparticles of extremely small size in the confined jet reactor can be achieved only if the
initial vapor concentration is significantly reduced or the jet velocity is increased. Reducing
the initial concentration results in a decrease in the synthesis productivity, and the velocity
increase has certain physical and technical limitations. Controlled change of nanoparticles
coagulation growth time in the thermal plasma flow manipulates the size of nanoparticles,
formed by the VLC mechanism. Additional channel to control the nanoparticle growth time
is fast quenching by cold gas injection. Cold gas injection forces cessation of the coagulation
growth after completion of vapor–liquid phase transition.

Distributed radial injection of quenching gas was organized at the periphery of the high-
temperature flow in the synthesis of alumina nanopowder by oxidation of a metal powder
in air plasma flow [25]. Quenching was carried out at the different distances from the reactor
inlet, thus varying the particles residence time in the coagulation growth zone. The change of
the injection gas flow rate and the injection position allowed the variation of the average par-
ticle size in the range of 35 to 75 nm. The obtained results indicate that confined DC plasma
jet reactor is capable to produce wide range of individual elements nanopowders as well as
nanopowders of inorganic compounds and composites.

6. Spheroidization of metal powders

Spherical powders with a particle size of the order of 10 μm are used as starting materials for
the manufacture of products from metals and alloys by the additive technologies methods.
Processing of powders with irregular particle shape in thermal plasma flows ensures their
fusion, leading to the formation of spherical particles [31].

Titanium powders (fractions of 40–70 μm and less than 40 μm) were processed in the flow
of thermal argon plasma, generated by an electric arc plasma torch. The hydrogenation-
dehydrogenation process produced raw titanium powders. After plasma processing, the degree
of spheroidization has reached 96%. Average sphericity coefficient was equal to 1.01 (Figure 7).
Experimental studies of the production of nonporous spherical powders of multicomponent
metal alloys have been performed. Ultrafine powder compositions of alloy components,
having a particle size of less than 1 μm, have been used as raw material. Model high-alloy
Fe-Ni-Cr alloy particles were used as example, and spherical alloy powders with particle sizes
in the range from 25 to 50 μm were produced.
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 17
http://dx.doi.org/10.5772/intechopen.76262

The process consisted of the following stages: microgranulation of ultrafine powder, heat
treatment of microgranules (drying at 100°C, removal of organic binder at 300°C, thermo-
chemical treatment in H2 at 1000°C, vacuum treatment at 1200°C), classification of heat-treated
microgranules with separation of microgranules fraction in the range 25 to 50 μm, spheroidi-
zation of the isolated fraction of microgranules in the thermal plasma flow, separation of

Figure 7. Micrographs of spheroidized titan powder.

Figure 8. Micrographs of granules. (А) – Initial alloy components, (В) – Spheroidized in plasma.
18 Powder Technology

the micron and submicron fraction. Micrographs of the alloy components microgranules and
particles, spheroidized in the plasma flow, are shown in Figure 8. The presented experimental
results indicate the possibility of metallic and alloys powders spheroidization in a confined
DC plasma jet apparatus using various initial powder materials.

7. Conclusion

The presented results of research and development testify to the wide possibilities of plasma
processes and devices for obtaining nanopowders of metals and their various inorganic com-
pounds with specified properties. The nanopowders, produced in the plasma reactors, were
used in various R&D projects aimed at creation of new materials with special and improved
properties. Along with the production of nanopowders, the same plasma reactor with confined
jet provides the possibility of metal and alloys powders spheroidizing for their application
in additive technologies. The accumulated experience is the basis for the creation of efficient
industrial production of powders using plasma reactors based on DC arc plasma torch.

Acknowledgements

This work was supported by the Fund of Applied Researches, Ministry of Education and
Science of the Russian Federation (unique identifier of the project RFMEFI57816X0216).

Author details

Andrey Samokhin1, Nikolay Alekseev1, Mikhail Sinayskiy1, Aleksey Astashov1,

Dmitrii Kirpichev1, Andrey Fadeev1, Yurii Tsvetkov1 and Andrei Kolesnikov2*
*Address all correspondence to: avkolesnikov@yahoo.com

1 A. Baikov Institute of Metallurgy and Materials Science (IMET RAS), Moscow, Russia

2 Tshwane University of Technology (TUT), Pretoria, South Africa

References

[1] Gogotsi Y, editor. Nanomaterials Handbook. 2nd ed. Boca Raton: CRC Press; 2006. p. 682
[2] Koch CC, editor. Nanostructured Materials: Processing, Properties and Applications.
2nd ed. Norwich: William Andrew; 2006. p. 784
[3] Wang ZL, Liu Y, Zhang Z, editors. Handbook of nanophase and nanostructured materi-
als. vol. IV, Berlin: Springer; 2002. p. 1200
[4] Shaw D, Liu B, editors. Handbook of Micro and Nanoparticle Science and Technology.
Berlin: Springer Verlag; 2007. p. 2400
 Nanopowders Production and Micron-Sized Powders Spheroidization in DC Plasma Reactors 19
http://dx.doi.org/10.5772/intechopen.76262

[5] Hosokawa M, Nogi K, Naito M, Yokoyama T, editors. Nanoparticle Technology Handbook.

2nd ed. Amsterdam: Elsevier; 2008. p. 730
[6] Liu LJ, Bashir S. Advanced Nanomaterials and Their Applications in Renewable Energy.
Amsterdam: Elsevier Science; 2015. p. 436

[7] Gromov AA, Korotkikh A G, Il'in A, DeLuca LT, Arkhipov VA, Monogarov KA, Teipel
U. Nanometals: Synthesis and Application in Energetic Systems. In: Energetic nanoma-
terials: Synthesis, characterization, and application. Amsterdam: Elsevier Science; 2016.
p. 47-63. DOI: 10.1016/B978-0-12-802710-3.00003-9

[8] Altavilla C, Ciliberto E, editors. Inorganic Nanoparticles: Synthesis, Applications, and

Perspectives. Boca Raton: CRC Press; 2010. p. 576

[9] Andrievski RA. Nanomaterials based on high-melting carbides, nitrides and borides.
Russian Chemical Reviews. 2005;74:1061-1072 https://doi.org/10.1070/RC2005v074n12
ABEH001202

[10] Toumanov YN. Plasma, High-Frequency, Microwave and Laser Technologies in Chem-
ical and Metallurgical Processes (in Russian). Moscow: Fizmatlit; 2010. p. 968

[11] TEKNANO Nanopowder Synthesis Systems. 2016. Available from http://www.tekna.

com/nanopowder-synthesis-systems

[12] Roth JR. Industrial Plasma Engineering, Volume 1: Principles. Boca Raton: CRC Press; 1995.
p. 339

[13] Zhukov MF, Zasypkin IM, Timoshevskii AN, Mikhailov BI, Desyatkov GA. Electric Arc
Generators of Thermal Plasma (in Russian). Nauka: Novosibirsk; 1999. p. 712

[14] Plasma Torches by Westinghouse Plasma Corporation. 2005. Available from https://
www.academia.edu/24044626/Plasma_Torches_by_Westinghouse_Plasma_Corporation

[15] Mikhailov BI. Electric-arc plasmachemical reactors of separated, single-chamber, and

combined types. Thermophysics and Aeromechanics (Teplophysica i aeromekhanika).
2010;17(3):425-440

[16] Samokhin AV, Astashov AG, Alekseev NV, Tsvetkov YV. Characteristics of heat and mass
transfer to the wall of a confined-jet plasma flow reactor in the processes of nanopowder
preparation from metals and their compounds. Nanotechnologies in Russia. 2016;11(1-2):
57-62. DOI: 10.1134/S1995078016010134

[17] Alekseev NV, Samokhin AV, Tsvetkov YuV. Plasma plant for manufacturing of nanodis-
persed powders (in Russian). RF Patent No 2311225. 2007

[18] Mädler L, Friedlander SK. Transport of nanoparticles in gases: Overview and recent
advances. Aerosol and Air Quality Research. 2007;7(3):304-342. DOI: 10.4209/aaqr.2007.
03.0017

[19] Sinayskiy MA, Samokhin AV, Alekseev NV, Tsvetkov YV. Extended characteristics
of dispersed composition for nanopowders of plasmachemical synthesis. Russian
Nanotechnologies. 2016;11(11-12):110-115. DOI: 10.1134/S1995078016060185
20 Powder Technology

[20] Granqvist CG, Buhrman RA. Ultrafine metal particles. Journal of Applied Physics.
1976;47:2200-2219. DOI: 10.1063/1.322870
[21] Kiss LB, Soderlund J, Niklasson GA, Granqvist CG. New approach to the origin of
lognormal size distributions of nanoparticles. Nanotechnology. 1999;10:25-28. DOI:
10.1088/0957-4484/10/1/006

[22] Alekseev NV, Balikhin IL, Kurkin EN, et al. Formation of ultrafine aluminum oxide
powder in confined air plasma jet (in Russian). Fizika I Khimiya Obrabotki Materialov
(Physics and Chemistry of Materials Processing). 1994;4-5:72-78
[23] Alekseev NV, Balikhin IL, Kurkin EN, Samokhin AV, Troitskaya EV, Troitskii VN.
Synthesis of titanium nitride and carbonitride ultradisperse powders in nitrogen plasma
jet (in Russian). Fizika I Khimiya Obrabotki Materialov (Physics and Chemistry of
Materials Processing). 1995;1:31-39
[24] Alekseev NV, Samokhin AV, Grechikov MI. Controlling the granulometric composi-
tion of the metal powders produced in plasma reduction processes (in Russian). Fizika
I Khimiya Obrabotki Materialov (Physics and Chemistry of Materials Processing).
1997;6:54-60

[25] Alekseev NV, Samokhin AV, Kurkin EN, Агафонов КН, Tsvetkov YV. Synthesis of alu-
mina nanoparticles by metal oxidation in thermal plasma flows (in Russian). Fizika I
Khimiya Obrabotki Materialov (Physics and Chemistry of Materials Processing). 1997;
3:33-39

[26] Alekseev NV, Samokhin AV, Tsvetkov YV. Synthesis of titanium carbonitride nanopow-
der by titanium tetrachloride processing in hydrocarbon-air plasma. High Energy
Chemistry. 1999;33(3):194-197
[27] Kolesnikov A, Alexeev N, Samokhin A. Controlled synthesis of alumina nanoparticles
in a reactor with self-impinging plasma jets. International Journal of Chemical Reactor
Engineering. 2007;5:A95. DOI: 10.2202/1542-6580.1521

[28] Samokhin AV, Polyakov SN, Astashov AG, Alekseev NV, YuV T. Simulation of
nanopowders synthesis in a jet type reactor. II. Formation of nanoparticles (in Russian).
Fizika I Khimiya Obrabotki Materialov (Physics and Chemistry of Materials Processing).
2014;3:12-17
[29] Samokhin AV, Sinayskiy MA, Alekseev NV, et al. Synthesis of nanoscale zirconium diox-
ide powders and composites on their basis in thermal DC plasma. Inorganic Materials:
Applied Research. 2015;6:528-535. DOI: 10.1134/S2075113315050172

[30] Kotlyarov VI, Beshkarev VT, Kartsev VE, et al. Production of spherical powders on
the basis of group IV metals for additive manufacturing. Inorganic Materials: Applied
Research. 2017;8(3):452-458. DOI: 10.1134/S2075113317030157
[31] Samokhin AV, Fadeev AA, Sinayskiy MA, et al. Fabrication of high-alloy powders
consisting of spherical particles from ultradispersed components. Russian Metallurgy
(Metally). 2017;7:547-553. DOI: 10.1134/S0036029517070138